Poly(phenylene oxide) plastic compositions containing bis-phenoxy flame retardants

ABSTRACT

Plastic compositions containing poly(phenylene oxide) and bisphenoxy compounds having the formula   WHEREIN Z is bromine or chlorine, m and m&#39;&#39; are integers having a value of 1-5, i and i&#39;&#39; are integers having a value of 0-2, R is herein defined and A is cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl or halobenzyl.

United States Patent [1 1 Anderson 1 POLY(PIIENYLENE OXIDE) PLASTIC COMPOSITIONS CONTAINING BIS-PHENOXY FLAME RETARDANTS [75] Inventor: Arnold L. Anderson, Alma, Mich.

[73] Assignee: Michigan Chemical Corporation, St.

Louis, Mich.

[ Notice: The portion of the term of this patent subsequent to May 14, 1991, has been disclaimed.

[22] Filed: Feb. 8, 1973 [21] Appl. No.: 330,857

Related US. Application Data [63] Continuationin-part of Ser. No. 260,240, June 6,

1972, abandoned.

[521 US. C1....260/45.9R;260/4595 G; 260/4575 R [51] Int. Cl C08q 51/60 [58] Field of Search... 260/459 R, 45.95 G, 613 B,

260/332 R, 2.5 A], DIG. 24; 106/15 PP [561 References Cited UNITED STATES PATENTS 3,385,819 5/1968 Gouinlock 260/4575 R [451 *July 1,1975

3,560,441 2/1971 Schwarcz' et a1. 260/457 R 3,658,634 4/1972 Yanagi et a1 161/403 3,717,609 2/1973 Kutner 260/4595 G Primary Examiner-M. .1. Welsh Attorney, Agent, or Firm-Jame's J. Mullen; Robert M. Phipps; Robert S. Frieman 57 ABSTRACT Plastic compositions containing poly(phenylene oxide) and bis-phenoxy compounds having the formula 14 Claims, No brawings 1 2. POLY(PHENYLENE OXIDE) PLASTIC Another object of the present invention is to provide COMPOSITIONS CONTAINING BlS-PHENOXY a material for poly(phenylene oxide) plastic compo'si FLAME RETARDANTS tions which will not substantially adversely effect the chemical and/or physical and/or mechanical properties This application is a continuation-in-part of copendof said compositions.

ing application Ser. No. 260,240, filed June 6, 1972 A further object ofthe present invention is to provide and now abandoned. The entire specification of this a flame retardant which is economic and easy to incorcase, Ser. No. 260,240, is to be considered as incorpop te into poly(phenylene oxide) plastics without rated herein by reference. being degraded or decomposed as a result of blending The prior art considered in conjunction with the 0 or processing operations. preparation of this application is as follows: US. Pat. It has been found that the foregoing objects can be Nos. 2,130,990; 2,186,367; 2,329,033; 3,666,692; obtained by the incorporation of a new class of bis- 3,686,320; 3,658,634; German Pat. Nos. 1,139,636; phenoxy compounds in PPO to subsequently provide 2,054,522; Japanese Pat. No. (72) 14,500 as cited in flame retarded compositions which exhibit outstanding Volume 77, Chemical Abstracts, column 153737k chemical, physical and mechanical properties. (1972); Chemical Abstracts, Volume 13, column 448-"; The bis-phenoxy compounds used in the present in- Chemical Abstracts, Volume 31, column 7045 and vention composition have the' formula:

A1 A l Zm I R o l Journal of the Chemical Society, pages 2972-2976 In Formula'l above, Z is bromine or chlorine, m and (1963). All of these publications are to be considered are nteg rs a independently aving a value of as incorporated her i b r f 1-5; iand i are integers each independently having a The present invention relates to plastic compositions Value of A is from the g p cyano nitl'o containing poly(phenylene oxide), (herein referred to z) lower alkoxy -gs 2 s)- lower as PPO), and certain bis-phenoxy compounds (hereinalkyl -g- 3 z s s r 4 9) fluorine y after defined) as flame retardants for said plastic comamino 'ga)2 2 5)z P y sa) positions halo-phenyl, benzyl (CH C H and halo-benzyl;

PPO plastics and utility thereof are known in the art n R 15 from the group as exemplified by Encyclopedia of Polymer Science and Technology Vol. 10, pages 92-111, John Wiley & Sons, Inc., New York, 1969 and which publication is in toto incorporated herein by reference.

The need for flame retarding PPO plastics has also been recognized in the art as exemplified by Encyclopedia of Polymer Science and Technology, ibid, pages 100 and 103.

The resultant disadvantages in the utilization of various prior art materials as flame retardants for PPO in- (e) CH2 C(O) CH clude, without limitation, factors such as thermal mi- I (f) gration, heat instability, light instability, non- H CH biodegradable, toxicity, discoloration and the large amounts employed in order to be effective. Thus, there is always a demand for a material which will function as a flame retardant in poly(phenylene oxides) and concurrently will not, by incorporation therein, ad-

versely effect the chemical and/or physical and/or me- (g) 2 CH where S :g chanical properties of the resultant poly(phenylene oxide) plastic composition.

The prior art problem of providing a flame retarded I F la I, i m or i m is not greater than 5. polyw y Oxide) composition having desired It is to be understood that all of the compounds fallchemical, physical and mechanical properties has MW ing within the above Formula I and as heretofore debeen substantially solved by the present invention and fined are generically described herein as bis-phenoxy the above-described disadvantages substantially overcompounds come. The bis'phenoxy compounds are found to be compat- Accordingly, one of the main objects of the present ible with and effective additives for various polymeric invention is to provide poly(phenylene oxide) plastic systems to make the resultant polymer flame retardant.

6 compositions which are flame retarded. lllustrative (but without limitation) of some of the Table l-Continued Compound No. Z m m A l l R 157 Br 3 3 -QCH,. 1 H c CH 1521 Br 2 2 c11.. 1 1 H2C CH 159 Br 2 2 F 1 1 1-1. .c CH

I60 Br 2 2 -N(c1-1 ,1 1 1 n c CH2 l6] Br 2 2 -(.,H 1 1 H, ,C C11,

162 Br 2 2 C,,H ,Br. 1 1 H. .c CH2 163 Br 2 2 (H2C,;H 1 1 H:C CH2 I64 Br 2 2 CH C H;,Br 1 1 H. ,C (H

165 Br 3 3 C,,H ,C1 1 1 rue (H2 166 c1 3 3 F 1 1 1-1. ,c CH

167 C1 2 2 CN 2 2 H,(? C'ri I68 Br 4 4 o o H c C11 I69 Cl 3 3 C H Br;, 1 1 11,0 CH;

170 CI 3 3 1 1o 2 2 11 C C11 171 c1 2 2 oc1-1,. 1 1 H2C CH,

172 c1 4 4 CH:, 1 1 H 0 CH 173 c1 3 3 F 2 2 H. .C c1-1 174 Br 1 1 c,1-1 1 1 up C1-1.

175 Br 1 1 oc,H,. 1 1 11 C c1-1.

water, a mixture of water and alcohol and a mixture of water and ketone) can be employed. The desired end product i.e. the bis-phenoxy compound, can be recovered from the reaction mass via various methods such as distillation or crystallization. Where the end product requires recovery via crystallization, various aromatic solvents such as benzene, toluene, xylene, dichlorobenzene and the like can be used.

Specifically, the bis-phenoxy compounds are prepared according to the following reactions:

on x-a-x -7 211x+ In the above reaction, X is halogen, preferably chlorine and R is the same as defined herein. Where In and m and i and i are different integers, then equivalent molar portions of the particular halogenated phenol are used with equivalent portions of dissimilar halogenated phenol.

The above reaction is conducted at temperatures ranging from the freezing point of the initial reaction mass to the boiling point thereof. Preferably the tem peratures are from about 40 C to about 200 C and more preferably from about 50 C to about 175 C. It is to be understood that the reaction can be conducted under sub-atmospheric (e.g. l/l-8/l0 atmospheres), atmospheric or superatmospheric (e.g. l.5lO atmospheres) pressure. Preferably, the reaction is carried out at atmospheric pressure.

The above-described processes can be carried out with conventional, readily available chemical processing equipment. For example, a conventional glass-lined vessel provided with heat transfer means, a reflux condenser and a mechanical stirrer can be advantageously utilized in practicing any of the preferred embodiments of the invention described in the examples set forth herein.

The amount of bis-phenoxy compound employed in the present invention compositions is any quantity which will effectively render the poly(phenylene oxide) containing composition flame retardant. In general, the amount used is from about I to 25% by weight, based on the total weight of the composition. Preferably, the amount employed is from about to about by weight. It is to be understood that any amount can be used as long as it does not substantially adversely effect the chemical and/or physical and/or mechanical properties of the end polymer composition. The amount utilized, however, is such amount which achieves the objectives described herein.

It is to be understood that the term poly(phenylene oxide) as used herein means products of the oxidative polymerization of phenols to poly(oxy phenylenes) which are also known as poly(phenylene oxides) or poly(phenylene ethers). This term also includes blends with other thermoplastics and/or plasticizers, however. the poly(phenylene oxide) comprises in all cases at least 50% by weight of the blend.

Thus the poly(phenylene oxide) used in the present invention compositions is any poly(phenylene oxide) herein defined and which one so desires to flame retard. It is to be understood that the poly(phenylene oxide) used can be a virgin" material, i.e. substantially free of additives such as stabilizers, plasticizers, dyes, pigments, fillers, and the like, or the poly(phenylene oxide) can have additives (such as those mentioned and described herein) already contained therein or added concurrently with or after the addition of the bisphenoxy compounds.

Another facet of the present invention relates to the use of certain metal compounds with the bis-phenoxy compounds to promote a cooperative effect therebetween and thus enhance the flame retardancy of the resultant plastic composition as compared to the flame retardancy of either one component used separately. These enhancing agents are from the group'antimony, arsenic, bismuth, tin and zinc-containing compounds. Without limitation, examples of said enhancing agents include Sb O SbCl SbBr Sbl SbOCl, AS203, As O ZnBO BaB O .H O, 2.ZnO.3B O -,.3.5-

H 0 and stannous oxide hydrate. The preferred enhancing agent is antimony trioxide.

The amount of enhancing agent employed in the present invention compositions is any amount which when used with said bis-phenoxy compounds will promote a cooperative effect therebetween. In general. the amount employed is from about 1 to about 15%, preferably from about 2 to about l07c, by weight, based on the total weight of plastic composition. Higher amounts can be used as long as the desired end result is achieved.

It is also within the scope of the present invention to employ other materials in the present invention compositions where one so desires to achieve a particular end result. Such materials include, without limitation, adhesion promoters; antioxidants; antistatic agents; antimicrobials; colorants; flame retardants such as those listed on pages 456-458, Modern Plastics Encyclopedia, ibid, (in addition to the new class of flame retardants described herein); heat stabilizers; light stabilizers; pigments; plasticizers; preservatives; ultraviolet stabilizers and fillers.

In this latter category, i.e. fillers, there can be mentioned without limitation, materials such as glass; carbon; cellulosic fillers (wood flour, cork and shell flour); calcium carbonate (chalk, limestone, and precipitated calcium carbonate); metal flakes; metallic oxides (aluminum, beryllium oxide and magnesia); metallic powders (aluminum, bronze, lead, stainless steel and zinc); polymers (comminuted polymers and elastomer-plastic blends); silica products (diatomaceous earth, novaculite, quartz, sand, tripoli, fumed colloidal silica, silica aerogel, wet process silica); silicates (asbestos, kaolimite, mica, nepheline syenite, talc, wollastonite, aluminum silicate and calcium silicate); and inorganic compounds such as barium ferrite, barium sulfate, molybdenum disulfide and silicon carbide.

The above mentioned materials, including fillers, are more fully described in Modern Plastics Encyclopedia, ibid, and which publication is incorporated herein (in toto) by reference.

The amount of the above described materials employed in the present invention compositions can be any quantity which will not substantially adversely effect the desired results derived from the present invention compositions. Thus, the amount used can be zero (0) percent, based on the total weight of the composition, up to that percent at which the composition can still be classified as a plastic. in general, such amount will be from about 0 to about and specifically from about I to about 50%.

The bis-phenoxy compounds can be incorporated in to the poly(phenylene oxide) at any processing stage in order to prepare the present invention compositions. In general, this is undertaken prior to fabrication either by physical blending or during the process of forming poly(phenylene oxide) per se. Where one so desires.

the bis-phenoxy compounds may be micronized intc,

finely divided particles prior to incorporation into the poly(phenylene oxide).

EXAMPLE I A poly(phenylene oxide) (PPO) plastic material (GE 534-801, a product of General Electric Company and containing substantially no fillers) is utilized as the base resin in order to prepare 26 formulations (plastit compositions). With the exception of formulation No l, the particular bis-phenoxy compound (and the antimony trioxide enhancing agent where indicated) is incorporated into the plastic by adding both to a Brabender mixer (Plastic-Corder, Torque Rheometer.

Model PLV-lSO, C. W. Brabender Instruments. Inc., Table ll.

TABLELII j FLAMMABILITY DATA FOR PPO PLASTIC COMPOSITIONS CONTAINING BlS-PHENOXY COMPOUNDS FORMULA- BIS-PHENOXY ENHANCING OXYGEN UL 94 TION COMPOUND AGENT INDEX No. NO. /1 817203. 71 7:

l. 0 0 25.5 SB 2. 2 20 0 29.0 SE-0 3. 2 20 38.5 SE-() 4. I9 0 27.0 SE-2 5. 19 20 10 36.0 SE0 6. 33 20 0 27.5 SE-2 7. 33 20 10 34.5 SE-O 8. 47 20 0 26.5 SE-2 9. 47 20 10 31.5 SE-O I0. 67 20 0 28.5 SE-I I l. 67 20 [0 37.5 SE-O I2. 83 20 0. 29.5 SE-() 13. 83 20 10 39.0 SE-O I4. 92 2O 0 28.0 SE-l I5. 92 20 I0 42.0 SE-() 16. I02 20 0 28.5 55-1 17. l02 20 10 36.0 SE-() 18. 1 I9 20 0 28.0 SE-l I9. I19 20 10 38.5 SE-O 20. I27 20 0 27.0 515-2 21. I27 20 I0 38.0 SE-O 22. I45 20 0 27.0 SE-2 23. I45 20 10 36.0 SE-() 24. I52 20 V 0 27.5 SE-2 25. I52 20 10 39.5 SE-0 26. 55 20 I0 40.5 SE-O South Hackensack, N.J.). The mixer is equipped with a pair of roller type blades positioned within a head provided with heat transfer means.

The resultant mixer is heated to about 320 C.; at this temperature, it is in a molten state. The percentages by weight of each component utilized in the respective formulations are listed in Table II. Each formulation is discharged from the mixer and upon cooling solidifies and is ground into chips. The chips are subjected to compression molding in a Wabash press by placing said chips between two platens, the bottom of which contains four equal size depressions three inches by five inches by /8 inch deep. The top platen is then placed over the bottom platen and heat transfer means sup-. plied thereto in order to melt said chips and thus provide solid samples (after cooling) for testing.

Portions of the samples of each respective formulation tNos. l-26) prepared according to the above described procedure are then subjected to two different standard flammability tests, i.e. UL 94 and ASTM D-286370. The UL 94 is, in general, the application of a burner to a test specimen (strip) for a certain period of time and observation of combustion, burning, and extinguishment. This procedure is fully set, forth in Underwriters Laboratories bulletin entitled UL 94. Standard for Safety, First Edition. September 1972 and which is incorporated herein by reference. ASTM No. D-2863-70 is a flammability test which correlates the flammability of a plastic specimen to the available oxygen in its immediate environment; this correlation is stated as an Oxygen Index. O.I., level predicated upon the percent oxygen in the gaseous medium which is required to just provide a steady state of continuous burning of the plastic specimen. This ASTM method is fully described in 1971 Annual Book of ASTM Standards Part 27, published by the American Society For Referring to Table II, the bis-phenoxy compound number relates to the structural formulae heretofor set forth in Table I; a difference of 2% in the Oxygen Index values is considered significant; anad the UL 94 values are on a graduated scale wherein the highest degree to lowest degree of flame retardancy is respectively SE-O, SE4, SE-2, SB and Burns.

The use of an enhancing agent such as Sb O to promote a cooperative effect between such agent and the bis-phenoxy compound is fully demonstrated via the results obtained from testing the odd numbered formulations. The highest UL 94 ratings and significantly higher 0.]. values are obtained by the use of an enhancing agent.

EXAMPLE 11 Example 1 is repeated twice; once using a 10% bisphenoxy compound level and 3% Sb- ,O level and secondly, l5% and 5% levels respectively. At both levels, the O.I. values and UL 94 ratings are slightly lower than the 20/10% levels of Example I.

i 13 EXAMPLE Ill Portions of the solid samples of Formulation Nos. 1-26 prepared according to the above described proce dure of Example I are subjected to the following ASTM tests in order to ascertain other properties of the resultant plastic composition:

Tensile Strength (at break) ASTM Test No. D638-6IT;

(2) Flexural Strength ASTM Test No. D790-63;

(3) Flexural Modulus ASTM Test No. D790-63;

(4) Notched Izod Impact ASTM Test No. D256-56; and (5) Heat Distortion formulation No. 1). Thus, there is no substantial adverse effect on the physical properties of the plastic material when the novel compounds are incorporated therein.

EXAMPLE IV The procedure of Examples I, II and III are repeated except that the enhancing agent used is zinc borate instead of Sb O Substantially the same results are obtained using zinc borate as those obtained using Sb O The other metal containing compounds are found to be equally effective.

EXAMPLE V Samples of each of Formulation Nos. 1 through 26 Table II, are subjected to temperature (thermal) stability tests via the use of thermal gravimetric analysis (TGA). This test employed the use of a Thermal Balance, model TGSl, Perkin-Elmer Corporation, Norwalk, Connecticut and an electrical balance, Cahn 2580 model, Cahn Instrument Company, Paramount, Calif. The results of these tests show that the bisphenoxy compound containing Formulations had more than adequate stability for melt processing and subsequent heat aging (i.e. high temperature applications) and thus demonstrating that the particular bis-phenoxy compounds are quite compatible with the plastic material. The bis-phenoxy compound stability thus aids in providing sufficient flame retardancy at the plastic decomposition temperature. This test also demonstrates that these compounds do not exhibit migration.

In view of the foregoing Examples and remarks, it is seen that the plastic compositions, which incorporate these compounds, possess characteristics which have been unobtainable in the prior art. Thus, the use of these compounds in the above described plastic material as flame retardants therefor is quite unique since it is not possible to predict the effectiveness and functionality of any particular material in any polymer system until it is actively undergone incorporation therein and the resultant plastic composition tested according to various ASTM Standardsj Furthermore, it is necessary, in order to have commercial utility. that the resultant flame retarded plastic composition possess characteristics such as being non-toxic. Use of these compounds in the plastic material has accomplished all of these obectives.

The above examples have been described in the fore going specification for the purpose of illustration and not limitation. Many other modifications and ramifications will naturally suggest themselves to those skilled in the art based on this disclosure. These are intended to be comprehended as within the scope of this invention.

I claim:

1. A plastic composition containing poly(phenylene oxide) having incorporated therein an effective amount of a flame retardant which is a compound having the formula:

wherein Z is selected from the group consisting of bromine or chlorine; m and m are integers having a value of 1-5; i and i are integers having a value of 0-2; A is selected from the group consisting of cyano, nitro, lower alkoxy, lower alkyl, fluorine, dialkylamino, phenyl, halo-phenyl, benzyl and halobenzyl; and R is selected from the group consisting of CH CH (e) CH C(O)CH (f) CH CH where S saturated ring CH 2. The composition as set forth in claim I wherein i and i are both 0.

3. The composition as set forth in claim 1 wherein i and i are both I.

4. The composition as set forth in claim 1 wherein i and i are both 2.

5. The composition as set forth in claim 3 wherein Z is bromine and A is cyano.

16 Z is bromine and A is dialkylamino.

11. The composition as set forth in claim 3 wherein Z is bromine and A is phenyl.

12. The composition as set forth in claim 3 wherein Z is bromine and A is halo-phenyl.

13. The composition as set forth in claim 3 wherein Z is bromine and A is benzyl.

14. The composition as set forth in claim 3 wherein 

1. A PLASTIC COMPOSITION CONTAINING POLY(PHENYLENE OXIDE) HAVING INCORPORATED THEREIN AN EFFECTIVE AMOUNT OF A FLAME RETARDANT WHICH IS A COMPOUND HAVING THE FORMULA:
 2. The composition as set forth in claim 1 wherein i and i'' are both
 0. 3. The composition as set forth in claim 1 wherein i and i'' are both
 1. 4. The composition as set forth in claim 1 wherein i and i'' are both
 2. 5. The composition as set forth in claim 3 wherein Z is bromine and A is cyano.
 6. The composition as set forth in claim 3 wherein Z is bromine and A is nitro.
 7. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkoxy.
 8. The composition as set forth in claim 3 wherein Z is bromine and A is lower alkyl.
 9. The composition as set forth in claim 3 wherein Z is bromine and A is fluorine.
 10. The composition as set forth in claim 3 wherein Z is bromine and A is dialkylamino.
 11. The composition as set forth in claim 3 wherein Z is bromine and A is phenyl.
 12. The composition as set forth in claim 3 wherein Z is bromine and A is halo-phenyl.
 13. The composition as set forth in claim 3 wherein Z is bromine and A is benzyl.
 14. The composition as set forth in claim 3 wherein Z is bromine and A is halo-benzyl. 